Compound of sulphureted oils



UNITED STATES ATENT OFFICE.

WALTER DQFIELD, OF MILLBURN, NEW JERSEY, ASSIGNOR TO THE TANNETTE MANUFACTURING COMPANY, OF NEWV JERSEY.

COMPOUND OF SULPHURETED OILS.

SPECIFICATION forming part of Letters Patent No. 473,306, dated April 19, 1892.

Application filed March 6, 1891. Serial No. 383,987. (No specimens.)

T0 ttZZ whom it may concern.-

Be it known that I, WALTER D. FIELD, a citizen of the United States, residing at Millburn, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Compounds of Sulphureted Oils; and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

My invention relates to that class of com pounds which are used alone or in combina tion with other elements as a coating for textile fabrics, paper, and leather, and for various other purposes too numerous to mention.

The object of the invention is to produce a compound that Will be stable and durable, not liable to decompose, oxidize, or evaporate, that will be proof against water and the action of the atmosphere, and that can be made very flexible, While at the same time having great body, when desired. To accomplish these results, I propose to use the sulphur derivatives or compounds of the glycyl or glyceryl ethers s of the unsaturated fatty acids, in combination nation with other elements.

This invention; however, consists of the composition of matter set forth above. The combination of this compound with other elements has been made the subject-matter of separate applications, which are divisions of this application and will hereinafter be referred to by date and number.

The pyroxyline or nitro-cellulose used in combination with the sulphur derivative or compound is of that grade or kind known in the arts as solublepyroxyline or nitrocellulose, and is obtained by subjecting vegetable fiber or cellulose to the action of nitric acid or of nitric and sulphuric acids, as is well understood, and before combining this nitrocellulose with the sulphur derivative or compound I would preferably dissolve the nitrocellulose in some solvent which would also be a solvent of the sulphur derivative or compound and then combine the same with the said sulphur derivative or compound, as hereinafter described.

In using the term sulphur derivatives or compounds of the glycyl or glyceryl ethers of the unsaturated fatty acids I mean all those compounds-such as sulphur-balsam-which are composed of glycyl or glyceryl ethers of the unsaturated fatty acids and sulphur, whether the sulphur be introduced directly or indirectly by the use of substances-such as sulphuric acid-from which practically all the sulphur can be extracted by processes similar-in results to those hereinafter to be described, the resultant of such a combination being a compound that is distinguished from the sulphur-chloride compounds in that it is soluble in benzine. In practice I have most frequently used those glycyl or glyceryl,

found olive-oil the best to use, and where a dark opaque substance is required cotton-seed oil. It is also proper to state that, while the sulphur derivative or compound may be produced by combining sulphur directly or indirectly with any of the oils of the class mentioned, yet the derivatives of some of these oilssuch as palm-oilwl1ich contain considerable proportions of the triglycerides of the saturated fatty acids are not as useful for all purposes as the derivatives of those oils which contain none or small proportions only of these triglycerides of the saturated fatty acids, and that other oils of this class of glycyl or glyceryl ethers of the unsaturated fatty acids which belong to what is chemically known as the linseed-oil group and are commonly known as drying-oils have the property when combined with sulphur of drying too rapidly when exposed to the air, and are therefore much less useful for mypurposesthan the otheroilsof the classabovementioned. WViththeseexceptions and explanations I know of none of the oils coming within the class of glycyl or glyceryl ethers of the unsaturated fatty acids which are not useful for the purposes of this invention.

hen sulphur is to be combined with glycyl or glyccryl ethers of the unsaturated fatty acids, I prefer the following method: The glycyl or glyceryl ether of the unsaturated fatty acids to be treated is first heated in any proper vessel to about 125 centigrade, at

which temperature an amount of sulphur, depending on the glycyl or glyceryl ether of the unsaturated fatty acid used, is slowly added and stirred into the glycyl or glyeeryl ether of the unsaturated fatty acid and the temperature of the mixture is raised to 210" centigrade, at which temperature the compound is kept for two or more hours. During this process of combining the sulphur and glycyl or glyceryl ether of the unsaturated fatty acid large quantities of sulphuretcd hydrogen are evolved, showing that the sulphur has entered into chemical combination with the glyeyl or glyceryl ethers of the unsaturated fatty acids; but I do not confine myself, however, to this exact method of producing my sulphur derivative or compound, as any other commercial method which will produce the same results may be used. I have found that in preparing this sulphur derivative or compound I could advantageously use an amount of sulphur from one-ninth to one-fifth the weight of the oil; but the proportion of sulphur which can be best used will be found to vary, depending on the oil used and on the degree of fluidity desired in the resulting compound, and I now give the proportions which I have found to produce the best results when used with the following oils ata temperature of about 210 centigrade to produce a compound of sirupy consistency when cold.

\Vith rape and castor oils it is best to use on e-ninth their weight of sulphur, with oil of sesame one-fifth its weight of sulphur, with olive oil and sperm-oil one-sixth theirweight of sulphur, with cod-liveroil and palm-oil oneseventh their weight of sulphur; but I do not confine myself to these exact proportions, as in some cases less and in some cases more sulphur may be used to advantage, depending in a large degree upon the fluidity of the compound desired, it being in all cases desirable to combine as much sulphur with the oil as it will absorb at about the temperature given and produce a product sufficiently liquid for the special use required, it being generally true that the lesser amount of sulphur prod uces a more liquid compound and the greater amount the more solid compound.

\Vhen the sulphur is to be added indirectly by the use of agents, such as sulphuric acid, the reaction when combined with said glycyl or glyceryl ethers of the unsaturated fatty acids produces substantially the same compound as when sulphur is added directly, but not of the same quality, as it contains as impurities other elements not found in the pure sulphur compound.

hen sulphur is to be combined indirectly by the use of sulphuric acid with glycyl or glyceryl ethers of the unsaturated fatty acids, I prefer to employ the following method: I add slowly to the glycyl or glyceryl ethers of the unsaturated fatty acid to be treated about one-fourth its weight of sulphuric acid of (36 Baum strength, takin g care that the temperature shall not rise above 40 centigrade. I then allow the mixture to stand from twelve to eighteen hours, then remove it from the vessel in which it was made and throw it gradually into a vessel containing three times its weight of well-cooled water, constantly stirring it until the compound rises to the surface of the water. I then draw off the water and thoroughly wash the remaining eompound and neutralize it with caustic soda. I then treat it with benzine to dissolve out the sulphur derivative or compound and recover said sulphur derivative or compound by evaporating the benzine. This sulphur derivative or compound is a body similar in its qualities to the sulphur derivative or compound formed of glycyl or glyceryl ethers of the unsaturated fatty acids and sulphur added directly; but when used is apt to produce a softer and less stable compound, and I therefore prefer to use the derivative or compound in which sulphur is added directly.

The sulphur derivative or compound is a neutral body insoluble in ethyl, methyl, or amyl alcohol (otherwise known as t'useloil) and water and soluble in chloroform, ether, benzole, benzine, amyl acetate, propyl acetate, and butyl acetate, and some other solvents and of a sirupy consistency when cold and fluid when hot. With this sulphur derivative or compound when cold I mix pyroxylinc, preferably first dissolved in some solvent which is also a solvent of the sulphur derivative and which will act harmoniously when introduced into the compound, and in the best practice adding the sulphur derivative in small quantities at a time and with constant sti rring, and I regulate the amount of pyroxyline to be added by the degree of flexibility desired in the resulting compound, it being true, so far as I have observed, that the lesser amount of pyroxyline gives the greater flexibility to the compound and the greater amount of pyroxyline the less flexibility, and herein lies one of the most useful features of my invention, as the pyroxyline and sulphur dcrivative or compound are harmonious when united in almost any proportions, thus enabling me to get great body in my compound by the use of the said sulphur derivative or com pound and still retain the useful qualities of the pyroxyline. In making flexible films or coatings for paper, leather, or textile fabrics I have found that the best compounds for that purpose contain from equal weights to three times as much sulphur derivative or compound as pyroxyline by weight. The solvent used should be of medium volatility, practically anhydrous and non-hygroscopic, and one which is not only a solvent of the pyroxyline and sulphur derivative separately, but will hold both in solution when mixed. I have used with favorable results and recommend the use of amyl acetate, propyl acetate, butyl acetate, and valerianate of amyl, and I may mix with them certain proportions of some harmonious non-solvent of nitro-cellulose or pyroxylinesuch as benzinefor the purpose of cheapening.

In using my compound in some of the arts pigments are added to give color or body, or both, to the resultant article. In practice I have found that adding more pigment than one-fourth to one-third of the weight of the pyroxyline is apt to lessen the strength of the compound when used in thin films or for coatings, and therefore when the compound is to be used for spreading or for films care should be taken not to add too much pigment, which should be thoroughly incorporated in the com-- pound before using.

For use in combination with textile fabrics, paper, and leather I have found that the following formula produces very excellent results: For a coating for textile fabrics, paper, and leather seven gallons butyl acetate, three gallons petroleum naphtha, fifteen pounds of pyroXyline, thirty to forty pounds of sulphur derivatives or compounds aforesaid, and one to two pounds of such pigment as may be required by'different colors. I have found the same formula to be well adapted for films when thinned down to the proper consistency for flowing by the addition of more of the floor-cloth or linoleum, with the addition, however, of large quantities of pigment or of ground wood, ground cork, or flock, or other like material to give substance.

In the place of butyl acetate in the above formula I have used mixtures of propyl and butyl acetate and also ,amyl'acetate.

' I do not herein claim a composition of matter consisting of glycyl or glyceryl ethers combined with sulphuric acid to form sulpho fatty acid compounds and proxyline of nitro-cellulose, as that forms the subject-matter of application, Serial No. 415,290, filed by me December 16, 1891.

What I claim as new is-- 1. A new composition of matter consisting of the sulphur derivatives or compounds of the glycyl or glyceryl ethers of the unsaturated fatty acids and soluble in benzine and pyroxyline or nitro-cellulose.

2. A new composition of matter consisting of the glycyl or glyceryl ethers of the unsaturated fatty acids, combined with sulphur to form sulphur-balsam and pyroxyline or nitro-cellulose.

In testimony that I claim the foregoing I have hereunto set my hand this 2d day of January, 1891.

WALTER D. FIELD.

Witnesses:

LEONARD RICHARDS, EDWARD W. BENJAMIN. 

